Bis-selenosemicarbazides

ABSTRACT

NEW BIS-SELENOSEMICARBAZIDES OF THE FORMULA   R1-N(-R2)-C(=SE)-N(-R3)-N(-R4)-CO-X-CO-N(-R5)-N(-R6)-   C(=SE)-N(-R7)-R8   WHEREIN EACH OF R1-R8 IS HYDROGEN ATOM OR AN AKYL, ARALKYL OR ARYL GROUP THERE BEING UP TO FOUR SUBSTITUENT GROUPS IN THE MOLECULE OF WHICH MAY BE ARYL OR ARALKYL GROUPS BUT ONLY TWO OF WHICH MAY BE ARYL OR ARALKYL GROUPS, AT LEAST ONE OF R1, R2, R3, R6, R7 AND R8 BEING A HYDROGEN ATOM AND X IS A DIRECT LINK OR A DIVALENT LINKING GROUP SELECTED FROM THE GROUP $CH2$N Y $CH2$M WHERE N AND M ARE EACH 0-5 AND Y IS $CH2)-, AN OXYGEN ATOM OR A SULPHUR ATOM OR A GROUP -NR9- WHERE R9 IS A HYDROGEN ATOM OR AN ALKYL, ARYL OR ARALKYL GROUP OR FROM A PHENYLENE OR NAPHTHALENE NUCLEUS ARE DESCRIBED.

United States Patent Oflic 3,819,698 Patented June 25, 1974 3,819,698 BIS-SELENOSEMICARBAZIDES John Colin Brown and Patrick Joseph Keogh, Ilford, England, assignors to Ilford Limited, Ilford, England No Drawing. Filed Dec. 17, 1971, Ser. No. 209,340 Claims priority, application Great Britain, Dec. 22, 1970, 60,802/ 70 Int. Cl. C07c 103/30 US. Cl. 260-558 H 4 Claims ABSTRACT OF THE DISCLOSURE New bis-selenosemicarbazides of the formula a r e? if a i" 2* N-C-N-N--X-C-N-N-C-N R2 R1; wherein each of R -R is a hydrogen atom or an alkyl, aralkyl or aryl group there being up to four substituent groups in the molecule of which all four may be alkyl groups but only two of which may be aryl or aralkyl groups, at least one of R R R R R and R being a hydrogen atom and X is a direct link or a divalent linking group selected from the group +cH2+ Y tCH -lm where n and m are each -5 and Y is {-CH an oxygen atom or a sulphur atom or a group NR where R is a hydrogen atom or an alkyl, aryl or aralkyl group or from a phenylene or naphthalene nucleus are described.

This invention relates to novel bis-selenosemicarbazides and to their production.

According to the present invention there is provided a bis-selenosemicarbazide of the general formula wherein each of Rf-R is a hydrogen atom or an alkyl, aralkyl or aryl group there being up to four substituent groups in the molecule of which all four may be alkyl groups but only two of which may be aryl or aralkyl groups, at least one of R R R R R and R being a hydrogen atom and X is a direct link or a divalent linking group selected from the group where n and m are each 0-5 and Y is CH,-, an oxygen atom or a sulphur atom or a group --NR where R, is a hydrogen atom or an alkyl, aryl or aralkyl group or from a phenylene or naphthalene nucleus.

Bis-selenosemicarbazides of formula (I) wherein each of R -R is a hydrogen atom or six or seven of R -R are hydrogen atoms the remainder being alkyl groups containing from 1 to 4 carbon atoms, Xis a direct link, a phenylene nucleus or a group (CH (CH where Y is -CH or S and m and n are each 0-2 are also provided.

Symmetrical bis-selenosemicarbazides of formula I are prepared by reacting two moles of a selenosemicarbazide of the general formula wherein each of Rr-Rg is a hydrogen atom or an alkyl, aralkyl or aryl group there being up to two substituent groups in the molecule of which each may be an alkyl group but only one of which may be an aryl or aralkyl group, with a dibasic acid chloride of the general formula ClCO-X-COCl wherein X has the meaning g1ven above.

Unsymmetrical bis-selenosemicarbazides of formula (I) are prepared by reacting a mole of a selenosemicarbazide of formula (IIa) or (IIb) with an acid chloride-half ester, preferably an acid chloride-half ester, of a dibasi acid of the general formula ClCOXCOOR wherein X has the meaning given above and R is an alkyl or aralkyl group, hydrolyzing the ester to form the free acid, and converting the acid to the acid chloride and reacting the latter with a mole of a selenosemicarbazide of formula (IIb) or (Ila) respectively, provided that in total there are not more than four substituent groups of which all four may be alkyl groups but not more than two may be aryl or aralkyl groups and at least one of R R and R or R R and R respectively in one of the selenosemicarbazide moieties is a hydrogen atom.

Unsymmetrical bis-selenosemicarbazides of formula (I) may also be prepared by reacting a selenosemicarbazide of formula (Ila) or (IIb) with an excess of a dibasic acid chloride and then reacting the unreacted acid chloride group with a selenosemicarbazide of formula (Hb) or (Ila) respectively.

The following dibasic acid chlorides are of use in the preparation of the bis-selenocarbazides of formula (I):

CHzCOCl COCl COCl

CHz-COCI The selenosemicarbazides of the above formulae (Ila) and (IIb) are known compounds as shown by the references set forth below.

The following formula (III) indicates the nitrogen atom referred to in the references.

l NHrNHfJ-NH (III) 4-phenylselenosemicarbazidepreparation described by Jensen & Frederiksen, Z. anorg. allgem. Chem. 230,

31-3 (1936). 2-phenylselenosemicarbazidepreparation described by Mautner & Kumler, J. Amer. Chem. Soc., 97-101 (1956). 4-ethylselenosemicarbazidepreparation described by Huls & Renson, Bull.s0c.chem.Belges, 65, 684- (1956). 4-propylselenosemicarbazide-preparation described by Colland-Charon, Huls & Renson, Bull.soc.chim.Belges,

71, 541-53 (1962). 1-phenylselenosemicarbazide and l-(p-tolyl) selenosemicarbazide-preparations described by Coland-Charon, Huls & Renson, Bull.soc.chim .Belges,

1-methylselenosemicarbazide, 2-methylselenosemicarbazide, 4-methylselenosemicarbazide, 1,1-dimethylselenosemicarbazide, 1,Z-dimethylselenosemicarbazide, 1,4-dimethylselenosemicarbazide and 1,2,4 trimethylselenosemicarbazide preparations described by Jensen, Fclbert, Pedersen & Svanhol, Acta chem Scand 20(1), 278-81 (1966). 2-methyl-4-phenylselenosemicarbazide, 4-(p-chlorphenyl) selenosemicarbazide and 4-(p-methoxyphenyl) selenosemicarbazidepreparations described by Bulka, Ahlens & Tucck, Chem. Ber., 100(4), 1373-8 (1967).

The bis-selenosemicarbazides of the present invention are of use as bleach-fix accelerators as described in our co-pending U.S. application Ser. No. 100,839 and when at least three of R R and at least three of R R are hydrogen atoms these compounds are of use as intermediates in the synthesis of bis-triazoleselenols as described in our co-pending application Ser. No. 209,339 (corresponding to British Application No. 60,801/70) filed on even date herewith.

EXAMPLE 1 Preparation of oxalyl-l,1'-bis(selenosemicarbazide) EXAMPLE 2 Preparation of terephthaloyl-l,1'-bis(selenosemicarbazide) When proceeding according to Example 1 but using thercphthaloyl chloride (4.1 g.) and selenosemicarbazide (5.5 g.) and heating the mixture to dissolve the acid chloride 4.0 g. of therephthaloyl 1,1 bis(selenosemicarbazide) m.p. 197-203 C. (decomp.) were obtained.

In the Example which follows a colour negative film was used which was made up as follows:

Layer Order and Silver Coating Weight in Sensitivity: mg. of Ag/decimetre Non Stress Blue Sensitive 13.4 Colloidal Silver Filled Layer Green Sensitive Topcoat 13.1 iIntralayer Green Sensitive Subcoat 16.0

Interlayer Red Sensitive Topcoat 17.5 Red Sensitive Subcoat 13.6

Base of cellulose triacetate Total 73.6

In this film: the blue sensitive layer contained a yellow colour coupler of the formula:

ornoQ-ooomoomrQ C isH'n-N-CHa COOH the green sensitive layers each contained a magenta colour coupler of the formula:

SOaH

The following processing solutions were used in Example 3.

Colour Developer G. Sodium metaborate Sodium sulphite anhydrous 2.0 Potassium bromide 1.0 Hydroxylamine sulphate 2.6 4-amino-N-ethyl N (fi-hydroxy ethyl)aniline sulphate 4.6 Water to 1 litre.

Stop-Fix Sodium thiosulphate pentahydrate g 171 Sodium acetate anhydrous g 31.4 Sodium sulphite anhydrous g 4.3 Acetic acid glacial ml 35 Potassium alum g 17.0 Ammonium chloride g 43 Water to 1 litre.

Bleach-Fix Disodium tetraborate decahydrate g 12.5 Boric acid g 22.5 Sodium hydroxide g 10.0 Ethylenediamine tetraacetic acid g 16.2 Disodium salt of ethylenediamine tetraacetic acid 3.5 Ferric chloride (60% w./w. solution) ml 15.0 Sodium thiosulphate pentahydrate g Sodium sulphite anhydrous g 4.0 Water to 1 litre.

Conditioner Disodium salt of ethylenediamine tetraacetic acid g 0.50 Sodium carbonate anhydrous g 4.5 Formaldehyde (40% w./v. solution) ml 10 Wetting agent (8% w./v. solution) ml 1.7

Water to 1 litre.

All processing solutions and wash water were used at 24 C.

Pieces of the colour negative film were fogged and processed in a number of processing sequences all containing the use of a bleach-fix bath. The metallic silver remaining in the film at the end of each processing sequence was measured by analysis and expressed in mg. of Agldecimetre When the bleach-fix bath or stop-fix bath contained one of the specified bleach-fix accelerators a reduction in the amount of residual silver resulted. The residual silver resulting when one of the accelerators was used is expressed as a percentage of that obtained when no accelerator was used (referred to as the control).

EXAMPLE 3 Pieces of the colour negative film were processed as follows:

Colour developer: minutes Stop-fix: 4 minutes with and without accelerator Bleach-fix: 6 minutes Wash: 4 minutes Conditioner: 4 minutes Wash: 4 minutes Dry.

The silver content of the pieces of film was analysed with the following results:

TABLE 1 Concentration of accelerator Residual silver in the stop-fix Accelerator Example bath in Percent of number mgJlitre MgJdm. control What we claim is: 1. A bis-selenosemicarbazide of the formula k i i i? f i i F f" /NLIN-N-X-(!JNN( JN\ Ra Rs wherein each of R -R is hydrogen, alkyl having 1-4 carbon atoms, phenyl, chlorophenyl, methoxyphenyl or tolyl, there being up to four such substituent groups other than hydrogen atoms in the molecule of which all four may be alkyl but only two may be phenyl, chlorophcnyl, methoxyphenyl or tolyl, at least one of R R R R R and R is hydrogen and X is a direct link, phenylene, naphthylene, or --(CH '--(CH where n and m are each zero or an integer of 1-5 and Y is NH, CH oxygen or sulfur.

2. A bis-selenosemicarbazide as defined in claim 1 wherein each of R R is hydrogen or six or seven of R -R are hydrogen, the remainder being alkyl containing 1-4 carbon atoms, X is a direct link, phenylene or (CH --Y (CH where Y is CH or S and m and n are each 1-2.

3. A bis-selenosemicarbazide according to claim 1, which is oxalyl-1,1'-bis(selenosemicarbaz.ide).

4. A bis-selenosemicarbazide according to claim 1, which is terephthaloyl-l,1'-bis(selenosemicarbazide).

References Cited UNITED STATES PATENTS 3,607,918 9/1971 Jurewicz 260558 HARRY I. MOATZ, Primary Examiner US. Cl. X.R. 

